Method of treating liquid hydrocarbons



Patented Aug- UNITED STATES} JOSEPH an) nuns, or PITTSBURGH, rnNNsYLvaNIA, ASSIGNOR 'ro CLARENCE r. v

PAT N OFFICE.

BYRNES, TRUSTEE, or sEwIcxLnY, PENNSYLVANIA.

mn'rnon or TREATING LIQUID HYnno'oARBoNs.

2N0 Drawing.

In connection with my copending applications, Serial No. 272,567, filed January 22, 1919, and Serial No. 435,355, filed January 6, 1921, I have found that by distilling orseparating the lighter hydrocarbons of the first run from the original product and then returning the remainder of this productand repeating the processunder certain conditions, I can obtain a considerable yield of lighter hydrocarbons suitable for use in internal combustion engines and of a new and better type than ordinary motor "spirit. I have also discovered that by introducing a basic oxide, preferably an oxide whose carbonate decomposes at a relatively low temerature, such as magnesium oxide, I can Ereak up the high molecular weight acids formed in connection with the obtain a cyclic method.

In carrying out the process, I first sub- 'ject thehydrocarbon, which may be anyfraction of mineral nil, such as .a kerosene fraction-or a product known in the art as pressure tar, or heavier fractions, to the catalytic partial combustion or partial oxidation method, fully described in the above recited applications. In this method, the liq- .uid hyrdocarbon is fed in measured quantities to a vaporizer where it is vaporized by heat, mixed with air which is admitted in regulated quantities, and the mixture is process and passed through a catalytic layer containing, for example, the complex oxides of mol bdenum, vanadium, uranium, etc. In t is method, I prefer to use a plurality of layers, introducing part of the total air used in the vaporizer, and a part between the screens, as in my copending application Se rial No. 435,355. The partially oxidized product is then condensed and consists of oxidized compounds running from alcohols through aldehydes to aldehyde acids. vI

then distill the lighter molecular weight ortionsof this product, up to, say, 200 8., which forms .a desirable engine fuel. If the heavier ortions of the product which remain are tien re-run through the apparatus, with an added portion of fresh oil 'fr'action, a further decomposition occurs and further motor spirit product is obtained. However, if these operations are repeated, I have found that the proportion of lighter hydrocarbons is reduced, the heavier molecular weight bodies building u as the process is repeated. 'But I have a so discovered and the proportion of .does not increase.

Application filed 31.11721, 1922. Serial No. 576,638;

that if, in re-running thematerial, I'decomose the or anlc acids b certain baslc ox-.

ides, I can providea continuousprocess in which there is a substantially constant production of lighter molecular weight portions heavier compounds ma esiurn oxide. Otherwise, the apparatusis t e same as shown in my copending application, Serial No. 435,355.

In the first run, the process was carried out the same as in the said applicatiomand I em loyed commercial Pennsylvania kerosene boilin between 200 G. and 300 C. After the first run, the condensed product was distilled u to 200 0., to obtain the lighter molecu arweight bodies, and the remaining heavier material was re-run through the a paratus, using about 56% of the oxidize oil from the previous run,

from which the light'products had been dis-' tilled,-and 44% oi the fresh oil.

The temperatures during'the run were as follows: Above the magnesium oxide layer and'the vaporizer before entering the screen,

the temperature was about 380 C. At thesuccessive screens inthe triple-screen apparatus, the successive temperatures were 340 C'. at the first screen; 350 (lat the second screen, and 350 C. at the third screen.

- Theoil mixture above described was introduced at the rate of 250 c. e. per minute, and the air was fed into the vaporizer at the rate of one cubic foot per minute. The air at screen No. 2 entered at the rate of .5 cu-- bic feet per minute, and at No. 3 screenat the rate of .5 cubic feet per minute. The carbon dioxide in the exit as averaged 3.7% .and the ox gen .8%, the atter showing .almost comp ete utilization of the oxygen introduced. i 3

In this run, 59.6 liters of the oil mixture were introduced, and the liquid product rei product collected from t an initial-distilling point coveredwas about 83% of this amount. The condenser ga've 125 (3., 23% of it distilling under 200 C. A rotary liquid pump was used in the circuit, this also serving as an agitating and scrubbing device, and the product collected therefrom, which represented one-fourth 'of the total product, gave an initial distilling point of 100 0., and 28.5% distilled under 200 C.

The product was again distilled up to 200 C. to remove the light material, the residual distilled product was mixed with the fresh oil in the same ratio as before and another run was made with all conditions the same, except that the vaporized temperature was lowered to about 340 C. and the oil feed cut down to 200 c. e. per minute. small amount of water, equal to 5%- of the oil feed, was introduced into the vaporizer.

This second run gave results practically the same as the first run. The yield was 83.9%, the condenser product showed an 0 initial distilling point of 92 0,23%- distilling under 200 0.; while the product collecting in the rotary water pump showed an initial distilling point at 82 (1., 27% of .it'distilling' under 200 C.

A. series of these tests have shown that this affords a practical process for preparing a low boiling point liquid fuel from heavier hydrocarbons.

In several runs, the percentage of light product obtained, based on the original oil fed'in, gave an average between and The fuel prepared in the above manner contains alcohols, aldehyde alcohols, aldehydes, ketones, ethers, aldehyde acids and hydrocarbons. The acids should be removed before the product is used in engines, and I also prefer to remove the more pungent aldehyde bodies present.

i I have found that this purification can be effected by adding about 5% of dry caustic soda to the lighter distilled-portions, heating to a gentle boiling under an invert condenser, for about three hours, andthen slowly distilling. The distilled product has an agreeable odor, and may be made practically water-white in color, if the caustic treatment be carried out-for a considerable period. .I

prefer to treat in this manner, removing the unpleasant aldehydic odors and leaving a.

product of a'- slightly yellow color, as the refining loss is less under these conditions and only amounts to about 10%. The mate'- rial taken out is substantially a soap.

Extensive automobile engine tests with this fuel have shown that such fuel possesses many advantages. The presence of oxidized bodies give the fuel the property of carrying full loads without detonation or knocking,- or with this action greatly reduced or practically eliminated. Furthermore, ,the

weight hydrocarbons result from presence of. the oxidized bodies which give more easy combustibihty make itpossible to 1 use a mixture of wider range in boiler points than is possible with a'straight hydrocarbon mixture. In other words, the end point of the mixture may be and preferably is car:

ried further than with ordinary motor spirit.

A .,composition of these oxidation products proceeds in two directionsone leading to the elimination of carbon monoxide and carbon dioxide with the formation of new hydrocarbons of lower carbon content, and the ide, the percentage of total recovery of light products is practically the same in each rerun wherethe same percentage of re-run .material is usedin connection with a certain percentage of fresh material.

My process therefore affords a new commercial method by which heavier hydrocarother consisting. in the breaking of the chains bons may be converted into lighter hydrocarbons with percentages of recovery which make the same commercially practicable.

The operations as carried on by me thus far have been at atmospheric pressure, althou h the pressure may be either below atmosp ere or above atmosphere; if desired.

The apparatus may be varied widely, a cat -alyst may or may not'be used, although I preferto employ the same, a single layer of catalytic material or-multiple layers may be employed, and many other changes may be made without departing from my invention.

I claim:

1. In the treatment of partially oxidized liquid hydrocarbons, the steps consisting of adding fresh hydrocarbon to at least a portion of the same, and subjecting the mixtureto a step of partial oxidation.

2. In the treatment of hydrocarbons, the steps consistin 'of partially oxidizingthe,

samewhile ely dividedcondition, sepa rating the lighter portion of the product, adding fresh hydrocarbon to the heavier portion, and again subjecting the same to the step of partial oxidation.

In the treatment of hyroearbons, the steps consisting of partially oxidizing'a hydrocarbon while in finely divided condition, fractioning out a lighter portion of.

again separating out a lighter portion of' the product. 7

5. In the treatment of hydrocarbons which already contain artificially-introduced chemically-combined oxygen, the steps consisting of adding fresh hydrocarbon thereto, thermally decomposing the same, and subjecting it to a partial oxidation step. v

(i. In the treatment of hydrocarbons which already contain artificially-introduced chemically-combined oxygen, the

steps consisting of adding a fresh portionof liquid hydrocarbon thereto, and subjecting the same in the vapor phase to thermal decomposition in' the presence of contact material.

7. In the treatment of liquid hydrocarbons, the steps consisting of subjecting the same in finely divided conditiontto a step of partial oxidation, separating out a lighter portion, mixing the heavier portion with a fresh portion of oil, subjecting the heavier portion mixture while in finely divided condition to a step of partial oxidation, again separating out a lighter portion of the product, and decomposing a portion of the product. 1

8. In the treatment of liquid hydrocarbons, the steps consisting of partially O'Xip dizing the saline while-in finely divided condition, separating out a lighter portion of the product, adding fresh hydrocarbon to the heavier portion, again partially oxidizing the same, and mixing the lighter portions thus obtained.

9. In the treatment of hydrocarbons which I already contain artificially introduced chemically combined oxygen, the steps-consisting of adding fresh hydrocarbon thereto, and subjecting the mixture to a step of partial oxidation.

10. In the treatment of hydrocarbons which already contain artificially-intro-v duced chemically-combined oxygen, the steps consisting of adding fresh hydrocarbon to the same and then thermally decomposing the mixture,

In testimony whereof I have hereunto set my hand. a

JOSEPH HIDY JAMES. 

